CN103012457B

CN103012457B - Halogenated organoaminosilane precursors and methods of depositing thin films comprising the same

Info

Publication number: CN103012457B
Application number: CN201210392207.9A
Authority: CN
Inventors: 萧满超; 雷新建; M·L·奥内尔; 韩冰; R·M·皮尔斯泰恩; H·钱德拉; H·R·伯文; A·德雷克斯凯-科瓦克斯
Original assignee: Versum Materials US LLC
Current assignee: Versum Materials US LLC
Priority date: 2011-09-27
Filing date: 2012-09-27
Publication date: 2018-02-09
Anticipated expiration: 2032-09-27
Also published as: JP2015026849A; EP2574611A1; CN107312028A; EP2574611B1; CN107312028B; KR101506940B1; KR20130034001A; TW201319077A; CN103012457A; US20130078392A1; US8993072B2; JP2013100262A; JP5658214B2; CN107857774A; JP6310018B2; TWI437005B; JP6100743B2; JP2016219834A

Abstract

Precursors and methods of forming thin films are described. In one aspect, a silicon precursor having the following formula I is provided: x _mR ¹ _nH _pSi(NR ²R ³) _{4‑m‑n‑p}I, wherein X is selected from C1, Br and I; r1 is selected from straight or branched chain C ₁‑C ₁₀Alkyl radical, C ₂‑C ₁₂Alkenyl radical, C ₂‑C ₁₂Alkynyl, C ₄‑C ₁₀Cycloalkyl and C ₆‑C ₁₀An aryl group; r ²Selected from straight or branched C ₁‑C ₁₀Alkyl radical, C ₃‑C ₁₂Alkenyl radical, C ₃‑C ₁₂Alkynyl, C ₄‑C ₁₀Cycloalkyl and C ₆‑C ₁₀An aryl group; r ³Selected from the group consisting of branched chains C ₃‑C ₁₀Alkyl radical, C ₃‑C ₁₂Alkenyl radical, C ₃‑C ₁₂Alkynyl, C ₄‑C ₁₀Cycloalkyl and C ₆‑C ₁₀An aryl group; m is 1 or 2; n is 0, 1 or 2; p is 0, 1 or 2; and m + n + p is less than 4, wherein R ²And R ³The linkage forms a ring or is not linked.

Description

The organic amino silane precursor of halo and the membrane deposition method comprising the precursor

The cross reference of related application

The application requires the priority of following application according to 35U.S.C.119：The U.S. that September in 2011 is submitted on the 27th is interim Application number 61/539,717, the content disclosed by it are integrally hereby incorporated herein by.

Background technology

It is described this document describes the organic amino silane precursor of the precursor that can be used for deposited dielectric films, particularly halo Dielectric film includes, but not limited to silicon-containing film such as silicon, amorphous silicon, crystalline silicon, microcrystal silicon, polysilicon, silicon nitride, oxygen SiClx, the silica of carbon doping, carbonitride of silicium and silicon oxynitride film.In another aspect, this document describes contain for depositing Purposes of the organic amino silane precursor of halo of silicon dielectric film in IC-components are manufactured.In these or others side Face, the organic amino silane precursor of halo can be used for a variety of depositing operations based on gas phase, include, but are not limited to ald (" ALD "), chemical vapor deposition (" CVD "), cyclic chemical vapor deposition (" CCVD "), plasma enhanced chemical vapor deposition (" PECVD "), low-pressure chemical vapor deposition (" LPCVD ") and aumospheric pressure cvd (" APCVD ") are heavy based on liquid Product technique, includes, but are not limited to spin coating, dip-coating, aerosol, ink-jet, silk-screen printing or jet deposition or thin film forming method.

A few class compounds can be used as the precursor of silicon-containing film (such as, but not limited to, silica or silicon nitride film).It is adapted to The example of these compounds as precursor includes silanes, chlorosilane, polysilazane class, amino silicone alkanes and azido silicon Alkanes.Inert carrier gas or diluent are also used for conveying precursor into reative cell (such as, but not limited to, helium, hydrogen, nitrogen etc.).

United States Patent (USP) 6,869,638 is described using the amino silane compounds of metal amide and following formula on substrate Form grid dielectric film such as grid dielectric, high-k metal oxide and ferroelectric metal oxides CVD methods： H_xSiA_y(NR¹R²)_4-x-y, wherein H is hydrogen；X is 0 to 3；N is nitrogen, each R¹And R²It is identical or different and independently selected from the following group：H、 Aryl, perfiuoroaryl, C₁-C₈Alkyl and C₁-C₈Perfluoroalkyl；And n is 1-6.Amino silicone described in No. 6,869,638 patents The example of alkane precursor includes two (diethylamino) dichlorosilanes and three (diethylamino) chlorosilanes.

WO 2011/123792, which describes to be formed by the combination of amino-metal precursor and halo metal precursor, contains metal-nitrogen ALD methods low temperature, based on heat or plasma of the film of compound, preferably from amino silane precursor and chlorosilane precursor Combination forms the film containing SiN.Described in the WO 2011/12792 applications comprising before amino chlorosilane and Aminoalkylsilanes The amino silane precursor of body, the amino chlorosilane have formula Cl_4-xSi(NR’R”)_x, wherein x=2 or 3, R ' and R " are independently Selected from H or alkyl, and R and R " can be connected to form ring structure, and the Aminoalkylsilanes precursor has formula R ' "_4-xSi(NR’ R”)_x, wherein x=1,2 or 3, R ' and R " can be connected to form ring structure, and R ' independently selected from H or alkyl, R ' and R " " be Alkyl having less than three carbon.

Bibliography " Substitution of chlorine in silicon tetrachloride Bydimethyl, diethylamino, and piperidino groups ", Breederveld etc., Research (London) 5：537-9 (1952) describes progressively replaces SiCl by using dialkyl amido₄In atom synthesize dialkyl amido chlorine silicon Alkane, so as to produce one or more following compounds：Diethyl amino base trichlorosilane, two (diethylamino) dichlorosilanes, three (diethylamino) chlorosilane or four (diethylamino) silane.Similar process is used to prepare piperidino trichlorosilane and two Piperidino dichlorosilane.

Bibliography " Molecular structures of some (dimethylamino) halogenosilanes in the gas phase by elec^trondiffraction and the crystal and molecular structures on mono-anddi-chloro(dimethylamino)silane by x-ray diffraction at Lowtemperatures ", Anderson etc., J.Chem.Soc., (1987) describe (dimethylamino) halogenated silanes SiH₂X (NMe₂), wherein X=Cl, Br or I.

Bibliography " Chloroaminosilanes.I.Preparation ofchloro (dimethylamino) Hydrogen silanes ", Washburne etc., Inorg.Nucl.Chem., 5 (1)：17-19 (1969) is described HSiCl₂NMe₂(I)、HSiCl(NMe₂)₂And HSi (NMe (II)₂)₃(III) preparation and the related chemistry of these compounds Matter.

Bibliography " Preparation of β-cyanoethyltrichlorosilane usingsilylamine Catalysts ", Pike etc., Journal of Organic Chemistry, 27 (6)：21-90-92 (1962) is described (CH₃)₃SiNR₂Type silylamine, it is proved to be directional catalyst by the way that trichlorosilane is added on acrylonitrile.The ginseng An example for examining the silylamine described in document be (ⁱPr₂N)SiCl₂H。

There is a need in the field to provide available for depositing silicon-containing films and provide the precursor of one or more advantages below：Low adds Work temperature (for example, 300 DEG C or less)；Relatively good sedimentation rate；Composition homogeneity and/or high-purity.

Invention summary

This document describes the organic amino silane precursor of halo and use it for being formed at least a portion of substrate and include The method of the film of silicon, silicon-containing film such as, but not limited to silicon thin film, silica, the silica of carbon doping, silicon nitride, oxynitriding Silicon, carborundum, carbonitride of silicium and combinations thereof.There is disclosed herein object to be processed (such as, for example, semiconductor die Piece) on form the method for dielectric film or coating.In an embodiment of methods described herein, the layer comprising silicon and oxygen exists Generate substrate on silicon oxide layer under conditions of, in settling chamber using the organic amino silane precursor of halo, optional one kind or A variety of other non-halogenated organic amino silane precursors and oxidant and deposit on substrate.In another of methods described herein In embodiment, under conditions of silicon nitride layer of the layer comprising silicon and nitrogen on generation substrate, before using halo in settling chamber Body, optional one or more non-halogenated organic amino silane precursors and contain nitrogen precursor and deposit on substrate.Further In embodiment, the organic amino silane precursor of halo as described herein be also used as metal-containing thin film (such as, but not limited to, Metal-oxide film or metal nitride film) dopant.It is as described herein with Formulas I in methods described herein The organic amino silane of halo is used as at least one and contains silicon precursor.

As understood by the skilled person, in Formulas I described herein, in R²And R³Link together with shape In the case of cyclization, R²Including being used for and R³The key (rather than hydrogen substituent) of connection, vice versa.Therefore, in R²And R³Connection Together to form ring in the case of, R²Selected from straight or branched C₁-C₁₀Alkylidene, C₃-C₁₂Alkenylene, C₃-C₁₂Alkynylene, C₄- C₁₀Cycloalkylidene and C₆-C₁₀Arlydene；R³Selected from side chain C₃-C₁₀Alkylidene, C₃-C₁₂Alkenylene, C₃-C₁₂Alkynylene, C₄-C₁₀It is sub- Cycloalkyl and C₆-C₁₀Arlydene.

In one aspect, the organic amino silane precursor of halo as described herein includes the silicon precursor with following formula I：

X_mR¹ _nH_pSi(NR²R³)_4-m-n-p I

Wherein X is the halogen selected from Cl, Br, I；R¹Independently selected from straight or branched C₁-C₁₀Alkyl, C₂-C₁₂Alkenyl, C₂- C₁₂Alkynyl, C₄-C₁₀Cycloalkyl and C₆-C₁₀Aryl；R²Selected from straight or branched C₁-C₁₀Alkyl, C₃-C₁₂Alkenyl, C₃-C₁₂Alkynyl, C₄-C₁₀Cycloalkyl and C₆-C₁₀Aryl；R³Selected from side chain C₃-C₁₀Alkyl, C₃-C₁₂Alkenyl, C₃-C₁₂Alkynyl, C₄-C₁₀Cycloalkyl and C₆-C₁₀Aryl；M is 1 or 2；N is 0,1 or 2；P is 0,1 or 2；And (m+n+p) and less than 4, and wherein R²And R³Connection is with shape Cyclization or R²And R³It is not connected to form ring.In some embodiments, the R in Formulas I²And R³Ring can be joined together to form. In other embodiments, the R in Formulas I²And R³It is not attached to and forms ring together.

In another aspect, the method that silicon-containing film is formed at least one surface of substrate is additionally provided, it includes：

At least one surface of the substrate is provided in the reaction chamber；With

By the depositing operation selected from chemical vapor deposition method and atom layer deposition process, the halogen with following formula I is used For organic amino silane precursor silicon-containing film is formed on described at least one surface：

X_mR¹ _nH_pSi(NR²R³)_4-m-n-p I

Wherein X is the halogen selected from Cl, Br, I；R¹Independently selected from straight or branched C₁-C₁₀Alkyl, C₂-C₁₂Alkenyl, C₂- C₁₂Alkynyl, C₄-C₁₀Cycloalkyl and C₆-C₁₀Aryl；R²Selected from straight or branched C₁-C₁₀Alkyl, C₃-C₁₂Alkenyl, C₃-C₁₂Alkynyl, C₄-C₁₀Cycloalkyl and C₆-C₁₀Aryl；R³Selected from side chain C₃-C₁₀Alkyl, C₃-C₁₂Alkenyl, C₃-C₁₂Alkynyl, C₄-C₁₀Cycloalkyl and C₆-C₁₀Aryl；M is 1 or 2；N is 0,1 or 2；P is 0,1 or 2；And (m+n+p) and less than 4, and wherein R²And R³Connection is with shape Cyclization or R²And R³It is not connected to form ring.In an embodiment of Formulas I, R²And R³It can be joined together to form Ring.In another embodiment of Formulas I, R²And R³It is not attached to and forms ring together.

In another aspect, there is provided silica is formed by atom layer deposition process or cyclic chemical vapor deposition technique The method of film, this method comprise the following steps：

A., substrate is provided in the reactor；

B. introduced into reactor and be selected from least the one of the organic amino silane precursor of at least one halo represented by following formula I Kind silicon precursor：

X_mR¹ _nH_pSi(NR²R³)_4-m-n-p I

Wherein X is the halogen selected from Cl, Br, I；R¹Independently selected from straight or branched C₁-C₁₀Alkyl, C₂-C₁₂Alkenyl, C₂- C₁₂Alkynyl, C₄-C₁₀Cycloalkyl and C₆-C₁₀Aryl；R²Selected from straight or branched C₁-C₁₀Alkyl, C₃-C₁₂Alkenyl, C₃-C₁₂Alkynyl, C₄-C₁₀Cycloalkyl and C₆-C₁₀Aryl；R³Selected from side chain C₃-C₁₀Alkyl, C₃-C₁₂Alkenyl, C₃-C₁₂Alkynyl, C₄-C₁₀Cycloalkyl and C₆-C₁₀Aryl；M is 1 or 2；N is 0,1 or 2；P is 0,1 or 2；And (m+n+p) and less than 4, and wherein R²And R³Connection is with shape Cyclization or R²And R³It is not connected to form ring；

C. purge gas purge is used；

D. oxygen source is introduced into reactor；

E. purge gas purge is used；With

Repeat step b to e is until film thickness desired by acquisition.

In a further aspect, there is provided silicon oxide film is formed at least one surface of substrate using CVD techniques Method, including：

A., substrate is provided in the reactor；

B. the organic amino silane precursor of at least one halo represented by following formula I is introduced into reactor：

X_mR¹ _nH_pSi(NR²R³)_4-m-n-p I

Wherein X is the halogen selected from Cl, Br, I；R¹Independently selected from straight or branched C₁-C₁₀Alkyl, C₂-C₁₂Alkenyl, C₂- C₁₂Alkynyl, C₄-C₁₀Cycloalkyl and C₆-C₁₀Aryl；R²Selected from straight or branched C₁-C₁₀Alkyl, C₃-C₁₂Alkenyl, C₃-C₁₂Alkynyl, C₄-C₁₀Cycloalkyl and C₆-C₁₀Aryl；R³Selected from side chain C₃-C₁₀Alkyl, C₃-C₁₂Alkenyl, C₃-C₁₂Alkynyl, C₄-C₁₀Cycloalkyl and C₆-C₁₀Aryl；M is 1 or 2；N is 0,1 or 2；P is 0,1 or 2；And (m+n+p) and less than 4, and wherein R²And R³Connection is with shape Cyclization or R²And R³It is not connected to form ring；With

C. oxygen source is provided with silicon oxide film at least one surface.

In another aspect, there is provided silicon nitride is formed by atom layer deposition process or cyclic chemical vapor deposition technique The method of film, this method comprise the following steps：

A., substrate is provided in the reactor；

B. at least one silicon precursor represented by following formula I is introduced into reactor：

X_mR¹ _nH_pSi(NR²R³)_4-m-n-p I

C. purge gas purge is used；

D. introduced into reactor and contain nitrogen source；

E. purge gas purge is used；With

Repeat step b to e is until silicon nitride film thickness desired by acquisition.

In a further aspect, there is provided silicon nitride film is formed at least one surface of substrate using CVD techniques Method, including：

A., substrate is provided in the reactor；

B. at least one organic amino silane precursor represented by following formula I is introduced into reactor：

X_mR¹ _nH_pSi(NR²R³)_4-m-n-p I

_cProvide and contain nitrogen source, wherein described at least one organic amino silane precursor and the reaction containing nitrogen source is siliceous to deposit On the film of nitrogen to described at least one surface.

In another aspect, this document describes the container for deposited dielectric films, there is Formulas I comprising one or more The organic amino silane precursor of halo.In a special embodiment, the container includes at least one equipped with appropriate The pressurisable container of valve and accessory (is preferably made of stainless steel), to allow to convey one or more precursors to being used for CVD or ALD In the reactor of technique.

In yet other aspects, there is provided for the composition of deposited dielectric films, it is included：

X_mR¹ _nH_pSi(NR²R³)_4-m-n-p I

Wherein X is the halogen selected from Cl, Br, I；R¹Independently selected from straight or branched C₁-C₁₀Alkyl, C₂-C₁₂Alkenyl, C₂- C₁₂Alkynyl, C₄-C₁₀Cycloalkyl and C₆-C₁₀Aryl；R²Selected from straight or branched C₁-C₁₀Alkyl, C₃-C₁₂Alkenyl, C₃-C₁₂Alkynyl, C₄-C₁₀Cycloalkyl and C₆-C₁₀Aryl；R³Selected from side chain C₃-C₁₀Alkyl, C₃-C₁₂Alkenyl, C₃-C₁₂Alkynyl, C₄-C₁₀Cycloalkyl and C₆-C₁₀Aryl；M is 1 or 2；N is 0,1 or 2；P is 0,1 or 2；And (m+n+p) and less than 4, and wherein R²And R³Connection is with shape Cyclization or R²And R³It is not connected to form ring；With the solvent being selected from the group：Ether, tertiary amine, nitrile, alkyl hydrocarbon, aromatic hydrocarbon, tertiary amino ether or Its mixture.

Brief Description Of Drawings

Fig. 1 provides mass spectrum (MS) figure of 2, the 6- lupetidine subbase dichlorosilanes described in embodiment 3.

Detailed description of the invention

The organic amino silane of halo is used as silicon-containing film that form stoichiometry and non-stoichiometric (for example, but unlimited In silicon, amorphous silicon, crystalline silicon, microcrystal silicon, polysilicon, silica, the silica of carbon doping, silicon nitride, silicon oxynitride and oxygen The film of carbonitride of silicium) precursor.These precursors are also used as the dopant for example for metal-containing thin film.Halo organic amino Base silane precursor is typically the volatile liquid precursor chemical of high-purity, and it is evaporated and is transported to settling chamber as gas Or to pass through CVD the or ALD process deposits silicon-containing films for semiconductor devices in reactor.In other embodiments, institute State the organic amino silane of halo to can be used in deposition or film forming method based on liquid, such as, but not limited to, spin coating, leaching Painting, aerosol, ink-jet, silk-screen printing or injection coating.Selection for the precursor material of deposition depends on wishing caused Jie Electric material or film.For example, precursor material can the content based on its chemical element, the stoichiometric proportion of its chemical element and/ Or the final dielectric film or coating that are formed under CVD and selected.Precursor material can also be for various other features such as Cost, non-toxic, operating characteristics, at room temperature keep liquid phase ability, volatility, molecular weight and/or other factorses and carry out Selection.In some embodiments, precursor described herein can by any mode, preferably use equipped with appropriate valve and The rustless steel container that pressurizes of accessory is transported to reactor assembly, to allow liquid phase precursor being delivered to settling chamber or reactor.

It is believed that compared with non-halogenated organic amino silane, the organic amino silane precursor of halo described herein can changed More preferable reactivity for substrate surface is provided during learning vapour deposition (particularly cyclic cvd deposition) or ald, With reacted via situ catalytic to be formed Si-N-Si keys, Si-Si bond, Si-O-Si keys and discharge organic amine and HCl, then organic amine Amine-hydrochloride is combined to form with HCl.It is believed that compared with the silicon precursor such as silicon tetrachloride or organic amino silane of routine, halo One particular advantage of organic amino silane is that halogen and organic amino can be with substrate surfaces during ALD or CCVD On Si_-OH or SiNH₂Reaction carrys out precursor described in grappling, so as to promote the deposition of silicon-containing film.Apart from the advantages described above, in example Such as using cyclic cvd, ALD or PEALD deposition process come in some embodiments of cvd silicon oxide or silicon nitride film, herein The organic amino silane precursor of the halo of description may can relatively low depositing temperature (for example, 500 DEG C or lower, 400 DEG C or It is lower or 300 DEG C or lower) under deposit highdensity material.In other embodiments, precursor described herein for example may be used For the deposition of the higher temperature at a temperature of about 500 DEG C-about 800 DEG C.

In one aspect, there is provided the precursor or the organic amino silane of halo represented by following formula I：

X_mR¹ _nH_pSi(NR²R³)_4-m-n-p I

Wherein X is the halogen selected from Cl, Br, I；R¹Independently selected from straight or branched C₁-C₁₀Alkyl, C₂-C₁₂Alkenyl, C₂- C₁₂Alkynyl, C₄-C₁₀Cycloalkyl and C₆-C₁₀Aryl；R²Selected from straight or branched C₁-C₁₀Alkyl, C₃-C₁₂Alkenyl, C₃-C₁₂Alkynyl, C₄-C₁₀Cycloalkyl and C₆-C₁₀Aryl；R³Selected from side chain C₃-C₁₀Alkyl, C₃-C₁₂Alkenyl, C₃-C₁₂Alkynyl, C₄-C₁₀Cycloalkyl and C₆-C₁₀Aryl；M is 1 or 2；N is 0,1 or 2；P is 0,1 or 2；And (m+n+p) and less than 4, and wherein R²And R³Connection is with shape Cyclization or R²And R³It is not connected to form ring.In some embodiments of the organic amino silane of halo of Formulas I, R²And R³It can connect It is connected together to form ring.In the alternate embodiments of the organic amino silane of halo of Formulas I, R²And R³It is not attached to shape together Cyclization.

In Formulas I-III and throughout the specification, term " alkyl " represents straight with 1-10 or 1-4 carbon atom Chain or pendant functional groups.Exemplary alkyl includes, but not limited to methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl Base, sec-butyl, the tert-butyl group, n-pentyl, isopentyl, tertiary pentyl, hexyl, isohesyl and new hexyl.In some embodiments, alkane Base can have one or more connected functional groups, such as, but not limited to, alkoxy, dialkyl amido or its combination. In other embodiments, alkyl does not have connected one or more functional groups.

In Formulas I-III and throughout the specification, term " cycloalkyl " represents there is 3-12 or 4-10 carbon atom Cyclic functionality.Exemplary cycloalkyl includes, but not limited to cyclobutyl, cyclopenta, cyclohexyl and cyclooctyl.

In Formulas I-III and throughout the specification, term " aryl " represents the aromatic ring with 6-12 carbon atom Shape functional group.Exemplary aryl includes, but not limited to phenyl, benzyl, chlorobenzyl, tolyl and ortho-xylene base.

In Formulas I-III and throughout the specification, term " alkenyl " is represented with one or more carbon-to-carbon double bonds and had There is the group of 2-12 or 2-6 carbon atom.Exemplary alkenyl includes, but not limited to vinyl or pi-allyl.

In Formulas I-III and throughout the specification, term " alkynyl " is represented with one or more carbon-to-carbon triple bonds and had There is the group of 2-12 or 2-6 carbon atom.

In Formulas I-III and throughout the specification, term " alkoxy " represents to be connected to oxygen atom and can have 1- The alkyl (for example, R-O) of 12 or 1-6 carbon atoms.Exemplary alkoxy includes, but not limited to methoxyl group (- OCH₃)、 Ethyoxyl (- OCH₂CH₃), positive propoxy (- OCH₂CH₂CH₃) and isopropoxy (- OCHMe₂)。

In some embodiments, one in the alkyl in Formulas I-III, alkenyl, alkynyl, alkoxy and/or aryl or Multiple groups can be substituted, or with the one or more atoms or atomic group for substituting such as hydrogen atom.Exemplary takes Dai Ji includes, but not limited to oxygen, sulphur, halogen atom (for example, F, Cl, I or Br), nitrogen and phosphorus.In other embodiments, Formulas I In one or more of alkyl, alkenyl, alkynyl, alkoxy and/or aryl can be unsubstituted.

In some embodiments, substituent R²And R³Connected in Formulas I to form ring structure.In other embodiments, Substituent R²And R³It is not connected in Formulas I.

Table 1 below provides some non-limiting examples of some embodiments of organic amino silane with Formulas I.

The exemplary organic amino silane with Formulas I of table 1.

In some embodiments, the organic amino silane of the halo of Formulas I as X and is selected from ClH comprising Cl₂Si(NR²R³) (wherein m=1, n=0, p=2, R²Selected from straight or branched C₃-C₁₀Alkyl and C₆-C₁₀Aryl, R³It is side chain C₃-C₁₀Alkyl or C₆-C₁₀Aryl, and wherein R²And R³Ring or alkyl-substituted ring can be formed) and R¹ClHSi(NR²R³) (wherein m=1, n=1, p =1, R¹It is C₁-C₁₀Alkyl and R²And R³It is straight or branched C₃-C₁₀Alkyl or C₄-C₁₀Aryl, and wherein R²And R³It can be formed Ring or alkyl-substituted ring).

In some embodiments, the organic amino silane of halo with Formulas I can be in organic solvent or solvent mixture By making the dichlorosilane (DCS) of 1 molar equivalent and the secondary amine of 1 molar equivalent or making trichlorosilane (TCS) and 1 or 2 mole ought The secondary amine with Formula Il of amount is reacted to prepare, and is absorbed using the tertiary amine such as triethylamine or tri-n-butylamine of 1 or 2 molar equivalents Byproduct hydrogen chloride, preferably use tertiary amine as shown in example 1 below and 2.In some embodiments, tertiary amine is worked as by equimolar The secondary amine of amount substitutes.There is Formula Il available for the selected secondary amine in the embodiment：

R²Selected from straight or branched C₁-C₁₀Alkyl, C₃-C₁₂Alkenyl, C₃-C₁₂Alkynyl, C₄-C₁₀Cycloalkyl and C₆-C₁₀Aryl； R³Selected from side chain C₃-C₁₀Alkyl, C₃-C₁₂Alkenyl, C₃-C₁₂Alkynyl, C₄-C₁₀Cycloalkyl and C₆-C₁₀Aryl, and wherein R²And R³Even Connect to form ring or R²And R³It is not connected to form ring.R wherein²And/or R³It is the reality of branched alkyl, cycloalkyl or aromatic group Apply in mode, the stability of the organic amino silane of the halo synthesized by these amine can be greatly improved, because amino and halogen atom Intermolecular substitution exchange reaction by this R²And/or R³The sterically hindered of group is hindered.Exemplary secondary amine bag with Formula II Include, but be not limited to：Diisopropylamine, di-iso-butylmanice, di-sec-butylamine, isopropylmethylamine, diisopropylethylamine, cyclohexyl methyl Amine, cyclopropylethylamin, Bicyclopropyl amine, cyclohexyl isopropylamine, methylphenylamine (phenyl methyl amine), N-ethylaniline (phenyl ethyl amine), N_-Isopropyl aniline, N- butylanilines, N- pi-allyls aniline, N- ethyls-meta-aminotoluene, N_-Methyl-adjacent first Aniline, N- methyl-p-toluidines, the fluoro- methylphenylamines of 4-, 4- chloro-n-methyls aniline, N- cyclohexyl aniline, 3- anilino-s third Nitrile or N- phenylamino acetonitriles.

With Formula II (wherein R₂And R₃Connection is to form ring) exemplary amine include, but are not limited to 2,6- dimethyl piperazines Pyridine, pipecoline, 2- crassitudes, 2,5- dimethyl pyrrolidines, 2,2,6,6- tetramethyl piperidines, 3- methyl indols, 2- Methyl indol, indoles, decahydroquinoline, 8- methyl isophthalic acids, 2,3,4- tetrahydroquinolines, 3- indole acetonitriles, 2- methyl indoline, 2,3- Indoline, 5_-Methyl indoline, 1,2,3,4- tetrahydroquinolines, 1,2,3,4- tetrahydrochysene -2- methylquinolines, 1,2,3,4- tetra- Hydrogen -6- methylquinolines, 3,4- dihydros -2H-1,4- benzoxazine, carbazole, 2,6- thebaines and 3,5- thebaine.

Following reaction equation 1,2 and 3, which provides, can be used for preparing the organic amino silicone of halo with Formulas I described herein The reaction process of alkane or the example of synthetic route.Reaction in reaction equation 1,2 and 3 can utilize organic solvent (for example, organic In the presence of solvent) carry out.In wherein the embodiment of organic solvent is used, the example bag of suitable organic solvent Include, but be not limited to, hydrocarbon (such as hexane, octane, toluene) and ether (such as diethyl ether and tetrahydrofuran (THF)).In these embodiments Or in other embodiment, reaction temperature is extremely used at about -70 DEG C in the range of the boiling point of solvent (if being related to solvent). Caused organic amino silane can be purified by the vacuum distillation after all accessory substances and solvent are removed.Reaction Formula 1-3 is the embodiment for the reaction for being related to dichlorosilane or trichlorosilane.It is related to the reality of the synthetic route of part aminating reaction Example is provided with embodiment 1 and 3 herein, and be related to can be via metal made from the reaction of amine and metal alkyl with Formula II The reaction equation 2 of amides provides in example 2.

Reaction equation 1

Reaction equation 2

Reaction equation 3

Method for forming siliceous dielectric film or coating is depositing operation.For the suitable heavy of method disclosed herein Product technique example include, but not limited to cyclic cvd (CCVD), MOCVD (metallorganic CVD), thermal chemical vapor deposition, etc. The change of gas ions enhancing chemical vapor deposition (" PECVD "), high density PECVD, photon assisted CVD, plasma-photon auxiliary Vapour deposition (" PPECVD "), low temperature chemical vapor deposition, the vapour deposition of chemical substance auxiliary, Hot Filament Chemical Vapor sink Product, the CVD of liquid polymer precursor, the deposition of supercritical fluid and low energy CVD (LECVD).In some embodiments, contain The film of metal passes through ald (ALD), plasma enhancing ALD (PEALD) or plasma enhancing cyclic cvd (PECCVD) process deposits.As used herein, term " chemical vapor deposition method " refers to wherein substrate exposed to one or more Any technique of the volatile precursor to be deposited desired by generation is decomposed with substrate surface reactions or on the surface of a substrate.As herein Self-limited type used, that term " atom layer deposition process " refers to the thin film deposition of material to the substrate with different compositions (self-limiting) (for example, the amount of the thin-film material deposited in each reaction cycle is constant) order surface chemistry is made With.Although precursor used herein, reagent and source can be described as " gaseous " sometimes, it should be understood that the precursor can be logical Cross the liquid or solid that directly evaporation, bubbling or distillation are transported under conditions of with or without inert gas in reactor Body.In some cases, the precursor of evaporation can pass through plasma generator.In one embodiment, using ALD techniques Deposited dielectric films.In another embodiment, using CCVD process deposits dielectric films.In further embodiment, Use hot CVD process deposits dielectric film.Terms used herein " reactor " includes, but are not limited to reative cell or settling chamber.

In some embodiments, method disclosed herein by using before reactor is introduced and/or during every ALD or CCVD from precursor avoid the pre-reaction of precursor.In this regard, the deposition technique such as ALD or CCVD techniques is used for Deposited dielectric films.In one embodiment, it is one or more containing silicon precursor, oxygen by the way that substrate surface is alternately exposed to Source, containing nitrogen source or other precursors or reagent and via ALD process deposits films.Film grows through the self-limited type control of surface reaction The pulse length and depositing temperature of system, each precursor or reagent are carried out.But once substrate surface saturation, film growth stop.

In some embodiments, method described herein further comprises except the halo organic amino with above-mentioned Formulas I One or more outside base silane precursor it is other contain silicon precursor or non-halogenated precursors.The other example bag containing silicon precursor Include, but be not limited to, organo-silicon compound such as type siloxane is (for example, HMDO (HMDSO) and dimethyl siloxane (DMS0)), organosilicon alkanes is (for example, methyl-monosilane, dimethylsilane, vinyl trimethylsilane, trimethyl silane, tetramethyl Base silane, ethylsilane, dimethylamino silane methylmethane, 2,4_-Two sila pentanes, the sila of Isosorbide-5-Nitrae-two butane, the sila hexanes of 2,5- bis-, The fluorinated derivatives of 2,2- dimethyl silanyl propane, 1,3,5- tri- Silinanes and these compounds), the organosilicon containing phenyl Compound (for example, dimethylphenylsilaneand and diphenylmethylsilane), oxygen-containing organo-silicon compound, such as dimethylformamide dimethyl oxygen Base silane, 1,3,5,7- tetramethyl-ring tetrasiloxanes, 1,1,3,3- tetramethyl disiloxane, 1,3,5,7- tetra- sila -4- oxos - Heptane, 2,4,6,8- tetra- sila -3,7- dioxos-nonane, 2,2- dimethyl -2,4,6,8- tetra- sila -3,7- dioxos-nonyl Alkane, octamethylcy-clotetrasiloxane, [1,3,5,7,9]-pentamethyl D5,1,3,5,7- tetra- sila -2,6- dioxos-ring Octane, hexamethyl cyclotrisiloxane, 1,3- dimethyldisiloxanes, 1,3,5,7,9- pentamethyl D5s, hexa methoxy The fluorinated derivatives of disiloxane and these compounds.

In a specific embodiment of approach described herein, the non-halogenated silicon precursor that contains is with following formula III compound：

(R²R³N)SiH₃(III)

Wherein R²Selected from straight or branched C₁-C₁₀Alkyl, C₃-C₁₂Alkenyl, C₃-C₁₂Alkynyl, C₄-C₁₀Cycloalkyl and C₆-C₁₀ Aryl；R³Selected from side chain C₃-C₁₀Alkyl, C₃-C₁₂Alkenyl, C₃-C₁₂Alkynyl, C₄-C₁₀Cycloalkyl and C₆-C₁₀Aryl, and wherein R²With R³Connect to form ring or R²And R³It is not connected to form ring.In some embodiments of formula III, R²And R³It can combine to be formed Cyclic group or ring.In the other embodiment of formula III, R²And R³Cyclic group or ring are not combined to form.It is non-halogenated it is siliceous before The example of body includes, but are not limited to：Two-isopropylamino silane, di-sec-butyl amino silane, phenylmethyl amino silane and 2,6- lupetidine subbase silane.

Depending on deposition process, in some embodiments, one or more halos or it is non-halogenated can be with containing silicon precursor It is introduced into predetermined mole (molar volume) or the micromoles of about 0.1- about 1000 in reactor.In this embodiment party In formula or other embodiment, halo or non-halogenated organic amino silane precursor can introduce reaction with predetermined time span In device.In some embodiments, the time span is about 0.001- about 500 seconds.

In some embodiments, formed to use in the presence of oxygen using oxygen source, oxygen containing reagent or precursor and retouched herein The dielectric film for the method deposition stated.Oxygen source can be introduced into reactor in the form of at least one oxygen source and/or can be attached Ground is present in other precursors for depositing operation.Suitable oxygen source gas can include, for example, water (H₂O) (for example, going Ionized water, purified water and/or distilled water), oxygen (O₂), oxygen plasma, ozone (O₃)、NO、NO₂, carbon monoxide (CO), dioxy Change carbon (CO₂) and combinations thereof.In some embodiments, oxygen source is included with the standard cubic centimeters per minutes of about 1- about 2000 The oxygen source gas that (squarecubic centimeter) (sccm) or about 1- about 1000sccm flow velocity are introduced into reactor Body.Oxygen source can introduce the about 0.1- times of about 100 seconds.In a special embodiment, oxygen source, which includes, has 10 DEG C or higher temperature water.In wherein film is by the embodiment of ALD or cyclic cvd process deposits, precursor pulse can With the pulse duration with more than 0.01 second, and oxygen source can have a pulse duration less than 0.01 second, and water Pulse duration can have the pulse duration less than 0.01 second.In yet another embodiment, blowing between pulse Horizontal pulse can continuously be entered with the purging between as little as 0 second or no pulse by sweeping the duration.Oxygen source or reagent with less than with The molecular amounts of 1: 1 ratio of silicon precursor provide, so as to which at least some carbon are retained in the dielectric film so deposited.

In some embodiments, dielectric film includes silicon and nitrogen.In these embodiments, using side described herein The dielectric film of method deposition is formed in the presence of containing nitrogen source.Reactor can be introduced in the form of at least one nitrogen source containing nitrogen source In and/or can be present in by way of parenthesis in other precursors for depositing operation.Suitable nitrogen containing source gas can include, example Such as, ammonia, hydrazine, monoalkylhydrazine, dialkyl group hydrazine, nitrogen, nitrogen/hydrogen, ammonia plasma treatment, nitrogen plasma, nitrogen/hydrogen plasma and its mixed Compound.In some embodiments, included containing nitrogen source with about 1 to about 2000 standard cubic centimeters per minute (sccm) or big Ammonia plasma treatment or hydrogen/Nitrogen plasma source gas that about 1 to about 1000sccm flow velocity is introduced into reactor.Can containing nitrogen source To introduce the time of about 0.1 to about 100 second.Film passes through ALD or the embodiment of cyclic cvd process deposits wherein In, precursor pulse can have the pulse duration more than 0.01 second, and can have the pulse less than 0.01 second containing nitrogen source Duration, and the pulse duration of water can have the pulse duration less than 0.01 second.In yet another embodiment In, the purging duration between pulse can continuously enter horizontal pulse with the purging between as little as 0 second or no pulse.

Deposition process disclosed herein can include one or more purge gas.For purging the reactant not consumed And/or the purge gas of byproduct of reaction is the inert gas not reacted with precursor.Exemplary purge gas includes, but It is not limited to, argon (Ar), nitrogen (N₂), helium (He), neon, hydrogen (H₂) and its mixture.In some embodiments, purge gas such as Ar The about 0.1-1000 seconds are fed in reactor with about 10 to about 2000sccm flow velocity, are likely to remain at instead so as to purge Answer the unreacting substance in device and any accessory substance.

Supplying precursor, oxygen source, the corresponding steps containing nitrogen source and/or other precursors, source gas and/or reagent can be by changing The time of these materials of change supply is carried out, to change the stoichiometric composition of obtained dielectric film.

Energy supply to precursor, containing at least one of nitrogen source, reducing agent, other precursors or its combination with induced reaction and Dielectric film or coating are formed on substrate.This energy can pass through (but not limited to) heat, plasma, pulse plasma Body, Helicon wave plasma (helicon plasma), high-density plasma, inductively coupled plasma, X ray, electronics Beam, photon, remote plasma process and combinations thereof provide.In some embodiments, the 2nd RF radio frequency sources can be used for changing The plasma characteristics become at substrate surface.It is related in wherein deposition in the embodiment of plasma, plasma occurs Method can include direct plasma method for generation (its plasma directly occurs in the reactor) or alternatively long-range Plasma method for generation (its plasma occurs and is fed in reactor outside reactor).

Organic amino silane precursor and/or other silicon precursors that contain can be transported to reative cell such as CVD or ALD in many ways Reactor.In one embodiment, liquid conveying system can be utilized.In alternative embodiment, synthesis can be used Liquid conveying and flash distillation process unit, such as, for example, by Shoreview, MN MSP Corporation manufactures Turbine evaporator (turbo vaporizer), to enable the material of low volatility quantitatively to convey, this causes reproducible Conveying and deposition are without the thermal decomposition of precursor.In liquid supplying way, precursor described herein can be in the form of neat liquid Conveying, or selectively, can be used with the solvent formulation comprising precursor or composition forms.Therefore, in some embodiment party In formula, when that may wish in given terminal applies and be favourable, precursor formulation can include the solvent with appropriate characteristics Composition on substrate to form film.

For the organic amino silane precursor of halo wherein with Formulas I to contain solvent and with Formulas I described herein The organic amino silane precursor of halo composition in those embodiments, selected solvent or its mixture not with it is organic Amino silane reacts.In composition the scope of the amount of solvent by weight percentage from 0.5 weight % to 99.5 weight % or From 10 weight % to 75 weight %.In this or other embodiment, described solvent has and the organic amino of halo of Formulas I Difference between the similar boiling point of silane boiling point (b.p.) or the boiling point of the boiling point of solvent and the organic amino silane of the halo of Formulas I It is 40 DEG C or smaller, 30 DEG C or smaller, 20 DEG C or smaller or 10 DEG C.Or the disparity range between boiling point has following Anticipate one or more end points：0th, 10,20,30 or 40 DEG C.The example of the OK range of boiling point difference includes, but are not limited to 0-40 DEG C, 20-30 DEG C or 10-30 DEG C.The example of suitable solvent includes, but are not limited in composition：Ether (such as Isosorbide-5-Nitrae-dioxane Hexane, dibutyl ethers), tertiary amine (such as pyridine, 1- methyl piperidines, 1- ethyl piperidines, N, N '_-Lupetazin, N, N, N ', N '- Tetramethylethylenediamine), nitrile (such as benzonitrile), alkyl hydrocarbon (such as octane, nonane, dodecane, ethyl cyclohexane), aromatic hydrocarbon (example Such as toluene, mesitylene), tertiary amino ether (such as double (2- dimethyl aminoethyls) ethers) or their mixture.Some are non- Restricted exemplified composition includes, but are not limited to：Include diisopropylaminoethyl silane (about 116 DEG C of boiling point) and octane (boiling point 125-126 DEG C) composition, include the combination of diisopropylaminoethyl silane (about 116 DEG C of boiling point) and pyridine (115 DEG C of boiling point) Thing, the composition comprising diisopropylaminoethyl silane (about 116 DEG C of boiling point) and toluene (110 DEG C of boiling point), include N- methyl cyclohexanes The composition of base amino silane (about 171 DEG C of boiling point) and decane (174 DEG C of boiling point), include the (boiling of N- methylcyclohexyls amino silane Point about 171 DEG C) and diethylene glycol dimethyl ether (162 DEG C of boiling point) composition, include N- isopropylcyclohexyls amino silane (boil About 199 DEG C of point) and pair (2- dimethyl aminoethyls) ether (189 DEG C of boiling point) composition, include N- isopropylcyclohexyl amino The composition of silane (about 199 DEG C of boiling point) and benzonitrile (191 DEG C of boiling point).

In another embodiment, this document describes the container for deposited dielectric films, it includes one or more tools There is the organic amino silane precursor of halo of Formulas I.In a special embodiment, container includes at least one equipped with appropriate Valve and accessory pressurisable container (being preferably made of stainless steel), to allow one or more precursors to be transported to for CVD or The reactor of ALD techniques.In this embodiment or other embodiment, the organic amino silane precursor of halo of Formulas I by There is provided in the pressurisable container that stainless steel is formed, and the purity of precursor is is 98% or higher or 99.5% or more by weight Height, this is suitable for most semiconductor application.In some embodiments, this container can also have described for mixing The device of precursor and one or more other precursors (if desired).In these embodiments or other embodiment, hold The content of device can be pre-mixed with other precursor.Selectively, the organic amino silane precursor of halo and/or other precursors can Be maintained at independent container in or with for maintaining machine amino silane precursor and other precursor isolations during storage Separating device single container in.In some embodiments, there is the organic amino silane precursor of halo of Formulas I also in container Comprising backfill gas (back fillgas), it is such as, but not limited to：Nitrogen, inert gas such as helium or its combination.Substituting Embodiment in, the container do not include backfill gas.

As described above, the purity level of the organic amino silane of halo is sufficiently high, to be enough to give birth to for reliable semiconductor Production is received.In some embodiments, the organic amino silane precursor of halo as described herein is included less than 2% weight or few Impurity below the one or more of 1% weight or less than 0.5% weight：Unhindered amina, free halide or halide ion and High molecular weight material.The higher degree of organic amino silane as described herein can be obtained by one or more following processes： Purifying, absorption and/or distillation.

In an embodiment of method described herein, can use cyclical deposition process such as CCVD, ALD or PEALD, wherein using be selected from Formulas I the organic amino silane precursor of halo at least one containing silicon precursor and optionally with Containing nitrogen source (such as, for example, ammonia, hydrazine, monoalkylhydrazine, dialkyl group hydrazine, nitrogen, nitrogen/hydrogen, ammonia plasma treatment, nitrogen plasma, Nitrogen/hydrogen plasma).

In some embodiments, connection precursor container is heated to one to the gas line of reative cell according to technological requirement Or multiple temperature, and the container of the organic amino silane precursor of halo with Formulas I is maintained at one or more temperature to be roused Bubble.In other embodiments, the solution comprising the organic amino silane precursor of at least one halo with Formulas I is injected into steaming Send out in device, the evaporator, which is maintained at one or more temperature, is used for direct liquid injection.

The air-flow of argon and/or other gases may be used as carrier gas to help to convey at least one and have during precursor pulse The steam of machine amino silane precursor is to reative cell.In some embodiments, reative cell operating pressure is about 1Torr.

In typical ALD or CCVD techniques, heated on the warm table of substrate (such as silicon oxide substrate) in the reaction chamber, institute Warm table is stated to be initially exposed to this and contain silicon precursor to be chemically adsorbed on substrate surface so as to obtain the compound.

Purge gas (such as argon gas) purges unadsorbed excessive compound from process chamber.After abundant purging, containing nitrogen source It can be introduced into reative cell to be reacted with the surface of absorption, then carry out another gas purging to remove dereaction by-product from the room Thing.Processing cycle can be repeated with film thickness desired by acquisition.

In some embodiments, the technique uses reducing agent.The reducing agent generally introduces in a gaseous form.Suitably The example of reducing agent include, but are not limited to：Hydrogen, hydrogen plasma, long-range hydrogen plasma (remote hydrogen Plasma), silanes (i.e. diethylsilane, ethylsilane, dimethylsilane, phenyl silane, silane, disilane, amino silicone Alkane, chlorosilane), boranes (i.e. borine, diborane), aluminium alkanes, germane class, hydrazine, ammonia or its mixture.For example depositing nothing Shape in a particular implementation of silicon, use reducing agent.

In this embodiment or other embodiment, it will be understood that can be with more the step of method described herein Kind order is carried out, can sequentially or simultaneously (for example, within least a portion time of another step) progress, and with above-mentioned Any combinations mode of mode is carried out.These materials can be supplied by changing by supplying the corresponding steps of precursor and nitrogen containing source gas Time span carry out, with the stoichiometric composition of dielectric film caused by change.

In another embodiment of method disclosed herein, formed and contained using the ALD deposition method comprised the following steps The film of silicon and nitrogen：

Substrate is provided in ALD reactors；

At least one organic amino silane precursor of halo represented by following formula I is introduced into ALD reactors：

X_mR¹ _nH_pSi(NR²R³)_4-m-n-p I

Chemisorbed at least one organic amino silane precursor of halo is on substrate；

The organic amino silane precursor of the unreacted at least one is purged with purge gas；

There is provided to organic amino silane precursor on the substrate of heating containing nitrogen source with organic with least one of absorption Amino silane precursors reaction；With

Optionally purge and any unreacted contain nitrogen source.

In another embodiment of method disclosed herein, formed and be situated between using the ALD deposition method comprised the following steps Conductive film：

Substrate is provided in the reactor；

At least one organic amino silane precursor of halo represented by following formula I is introduced into reactor：

X_mR¹ _nH_pSi(NR²R³)_4-m-n-p I

The organic amino silane precursor of the chemisorbed at least one is on substrate；

Oxygen source is provided with least one organic amino with absorption to organic amino silane precursor on the substrate of heating Base silane precursors reaction；With

Optionally purge any unreacted oxygen source.

Above-mentioned steps define a circulation for method described herein, and the circulation can be repeated until being wished The dielectric film thickness of prestige.In this embodiment or other embodiment, it will be understood that the step of method described herein Can be carried out with a variety of orders, can sequentially or simultaneously (for example, within least a portion time of another step) carry out, Any combinations mode in the above described manner is carried out.These things can be supplied by changing by supplying the corresponding steps of precursor and oxygen source The time span of matter is carried out, with the stoichiometric composition of dielectric film caused by change, although always with less than relative to The amount of the stoichiometry of available silicon uses oxygen.

For multicomponent dielectric film, other precursors containing silicon precursor, containing nitrogen precursor, reducing agent or other reagents as that can hand over Alternately it is introduced into reative cell.

In the further embodiment of method described herein, hot CVD process deposits dielectric film is used.In this reality Apply in mode, this method includes：

One or more substrates are placed in be heated to from environment temperature to about 700 DEG C of temperature and be maintained at 1Torr or In reactor under lower pressure；

Introduce the organic amino silane precursor of at least one halo with following formula I：

X_mR¹ _nH_pSi(NR²R³)_4-m-n-p I

Oxygen source is provided into reactor with amino silane precursors reaction organic with least one at least in part and to deposit Dielectric film is on one or more substrates.In some embodiments of the CVD method, reactor is introducing step process In be maintained under 100mTorr to 600mTorr pressure.

Above-mentioned steps define a circulation for method described herein, and the circulation can be repeated until being wished The dielectric film thickness of prestige.In this embodiment or other embodiment, it is possible to understand that the step of method described herein Can be carried out with a variety of orders, can sequentially or simultaneously (for example, within least a portion time of another step) carry out, Any combinations mode in the above described manner is carried out.These things can be supplied by changing by supplying the corresponding steps of precursor and oxygen source The time span of matter is carried out, with the stoichiometric composition of dielectric film caused by change, although always with less than relative to The stoichiometry of available silicon uses oxygen.

For multicomponent dielectric film, other precursors are such as containing silicon precursor, containing nitrogen precursor, oxygen source, reducing agent and/or other examinations Agent can be alternately introduced in reative cell.

X_mR¹ _nH_pSi(NR²R³)_4-m-n-p I

There is provided into reactor and contain nitrogen source down to partially amino silane precursors reaction organic with least one and sink Dielectric film is accumulated to one or more substrates.In some embodiments of the CVD method, reactor is introducing step mistake It is maintained in journey under 100mTorr to 600mTorr pressure.

As described above, to can be used for utilizing more than a kind of precursor (such as described herein with Formulas I for method described herein The organic amino silane of halo) and other precursor (such as before non-halogenated organic amino silane described herein with formula III Body), those and/or chlorosilane for example described herein containing silicon precursor be (such as, but not limited to a chlorosilane (MCS), dichlorosilane (DCS), trichlorosilane or silicon tetrachloride) and/or alkylchlorosilane (such as, but not limited to methylchlorosilane, ethyl chlorosilane, Dimethyl dichlorosilane (DMCS), ethyl dichlorosilane) carry out deposition film.In these embodiments, depending on used different precursors Number, one or more precursors are described as the first precursor, the second precursor, the 3rd precursor etc..This method for example available for In cyclic chemical vapor deposition or ald.In these or other embodiments, the precursor can be with a variety of sides Formula introduces (for example, a) and introduces the first precursor；B) purge；C) the second precursor is introduced；D) purge；E) the 3rd precursor is introduced；F) purge Deng, or, a) introduce the first precursor；B) purge；C) the second precursor is introduced；D) purge；E) the second precursor is introduced；Deng).At one In specific embodiment, there is provided silicon oxide film or silicon, the method for carbon and sull, comprise the following steps：

A) steam as caused by the first precursor and substrate contact first precursor described in chemisorbed heated are made to heating Substrate on；

B) any unadsorbed precursor is purged；

C) to introducing oxygen source on the substrate of heating with the first precursors reaction with absorption；

D) any unreacted oxygen source is purged；

E) steam as caused by the second precursor different from the first precursor and the substrate contact heated are made with chemisorbed institute The second precursor is stated to the substrate of heating；

F) any unadsorbed precursor is purged；

G) to introducing oxygen source on the substrate of heating with the first and second precursors reactions with absorption；With

H) any unreacted oxygen source is purged,

Wherein repeat step a) is to h) until reaching desired thickness.

In the yet another implementation of approach described herein, there is provided deposited silicon nitride or carbon silicon nitride film Method, comprise the following steps：

B) any unadsorbed precursor is purged；

C) to introducing nitrogen source on the substrate of heating with the first precursors reaction with absorption；

D) any unreacted nitrogen source is purged；

F) any the second unadsorbed precursor is purged；

G) to introducing nitrogen source on the substrate of heating with the second precursors reaction with absorption；With

H) any unreacted nitrogen source is purged,

Wherein repeat step a) is to h) until reaching desired thickness.

In further embodiment, described herein is to use cyclic chemical vapor deposition (CCVD) or atomic layer Deposition (ALD) technology is such as, but not limited to plasma enhancing ALD (PEALD) or plasma enhancing CCVD (PECCVD) technique Carry out the method for depositing silicon-containing films.In these embodiments, depositing temperature can be with of a relatively high, or is about 500 DEG C_-800 DEG C, So as to control the specification of the film performance needed for particular semiconductor application.In a specific embodiment, methods described Comprise the following steps：Steam and the substrate contact of heating as caused by the organic amino silane of the halo with Formulas I is set to be inhaled with chemistry The attached precursor is on the substrate of heating；Purge any unadsorbed precursor；Reducing agent is introduced with the precursor of reduction adsorption；With Purge any unreacted reducing agent.

In some embodiments, the organic amino silane precursor of the halo described herein with Formulas I is also used as containing The dopant of metallic film (such as, but not limited to, metal-oxide film or metal nitride film).In these embodiments In, using ALD or CVD techniques (those techniques as described herein), have using metal alkoxide, metal amide or volatility Machine metal precursor deposits metal-containing thin film.Can be used for the example of the suitable metal alkoxide precursor of method described herein includes, But be not limited to, 3-6 races metal alkoxide, have alkoxy and alkyl-substituted cyclopentadienyl ligands 3-6 races metal complex, 3-6 races metal complex with alkoxy and alkyl-substituted pyrroles's ylidene ligands, with alkoxy and diketone root (diketonate) the 3-6 races metal complex of part, the 3-6 races metal complex with alkoxy and ketone ester part；Can be with Example for the suitable metal amides precursor of method described herein includes, but not limited to four (dimethylamino) zirconiums (TDMAZ), four (diethylamino) zirconiums (TDEAZ), four (ethylmethylamino) zirconiums (TEMAZ), four (dimethylamino) hafniums (TDMAH), four (diethylamino) hafniums (TDEAH) and four (ethylmethylamino) hafniums (TEMAH), four (dimethylamino) titaniums (TDMAT), four (diethylamino) titaniums (TDEAT), four (ethylmethylamino) titaniums (TEMAT), (diethyl of tertbutylimido three Base amino) tantalum (TBTDET), tertbutylimido three (dimethylamino) tantalum (TBTDMT), (the ethyl first of tertbutylimido three Base amino) tantalum (TBTEMT), ethylimino three (diethylamino) tantalum (EITDET), ethylimino three (dimethylamino) Tantalum (EITDMT), ethylimino three (ethylmethylamino) tantalum (EITEMT), tertiary pentyl imino group three (dimethylamino) tantalum (TAIMAT), tertiary pentyl imino group three (diethylamino) tantalum, five (dimethylamino) tantalums, (the ethyl first of tertiary pentyl imino group three Base amino) tantalum, two (tertbutylimido) two (dimethylamino) tungsten (BTBMW), two (tertbutylimido) two (diethyl amino Base) tungsten, two (tertbutylimido) two (ethylmethylamino) tungsten and combinations thereof.It can be used for the suitable of method disclosed herein The example of Organometallic precursor include, but not limited to 3 race's metal cyclopentadienyl compounds or alkyl cyclopentadienyl compound. This paper exemplary 3-6 races metal include, but not limited to Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Er, Yb, Lu, Ti, Hf, Zr, V, Nb, Ta, Cr, Mo and W.Other volatile organometallic precursors include, but are not limited to metal alkyl precursor for example, but It is not limited to triethyl aluminum (TEA), trimethyl aluminium (TEA).

In some embodiments, the organic amino silane of the halo can be used for the deposition based on liquid or the film side of being formed Method, such as, but not limited to, spin coating, dip-coating, aerosol, ink-jet, silk-screen printing or injection coating.Wherein silicon thin film by based on In the embodiment that the deposition of liquid is formed, laminated film is by particularly comprising as at least one siliceous of silica source The composition of the organic amino silane of the precursor such as halo as described herein with Formulas I, catalyst and water is formed.The composition Solvent and surfactant can also be included.In short, simultaneously evaporation solvent and water can be formed on substrate by composition distribution Film.Surfactant, residual solvent and water generally are enough to generate by making the substrate of coating contact with one or more energy The time of silicon-containing film removes.In some cases, the film can be preheated so as to be substantially finished the water of silica source Solution, continue cross-linking process and drive away any residual solvent (if present) from film.

In addition to the organic amino silane of the halo with Formulas I described herein, another example of silica source can be with It is included in the compound that Si -- H bond is produced when removing pore-forming material.

The further example in the source is seen such as bibliography Hay, " Synthesis ofOrganic- Inorganic Hybrids via the Non-hydrolytic Sol-Gel Process ", Chem.Mater., 13, 3396-3403 (2001) or Hay etc., " A Versatile Route toOrganically-Modified Silicas and Porous Silicas via the Non-HydrolyticSol_-Gel Process ", J.Mater.Chem., 10,1811- In non-hydrolytic chemistry methods described in 1818 (2000).

Another example again of silica source can include cataloid, fumed silica or silicic acid starting material Material.

Still other example of silica source includes silsesquioxane, such as hydrogen silsesquioxane (HSQ, HSiO₁.₅) and Methyl silsesquioxane (MSQ, RSiO_1.5, wherein R is methyl).

In some embodiments, can be added to silica source as hydrolysis and condensation product in mixture.Two The hydrolysis and condensation of silica source by intermittently or continuously added to solvent and adding titanium dioxide simultaneously by water and catalyst Silicon source, and carried out while being usually and stirring the mixture 0-24 hours at a temperature of -30-100 DEG C, preferably 20-100 DEG C Hydrolysis and condensation reaction and occur.The composition can be adjusted with by being concentrated in each preparation process or dilute with solvent Release to provide desired solids content.In addition, the compound of acetic acid is produced when silica source can be hydrolysis.

Any point during film is formed can occur for the hydrolysis and condensation of silica source, i.e. added to mixing Before thing, be added to mixture after, contacted with least one energy before and/or period etc..For example, in some embodiments In, at least one silica source is mixed with solvent, water and surfactant in a reservoir, and catalyst is gradually added into container In and mix.It is expected that a variety of different orders can be used to be added in mixture without departing from the spirit of the invention.

Catalyst suitable for the present invention includes that the substituent water from silica source can be catalyzed in presence of water The condensation of two kinds of silica sources of solution and/or catalysis is to form any organic or inorganic acid of Si-O-Si bridges or alkali.Catalyst can To be organic base, such as, but not limited to quaternary ammonium salt and hydroxide, such as ammonium or tetramethylammonium；Amine, such as primary amine, secondary amine and uncle Amine；And amine oxide.Catalyst can also be acid, such as, but not limited to nitric acid, maleic acid, oxalic acid, acetic acid, formic acid, glycolic, second Aldehydic acid or its mixture.In a preferred embodiment, the catalyst includes nitric acid.

It can include that there is deliquescent any solvent to reagent suitable for the solvent of the present invention.Solvent for example can be alcohol Solvent, ketone solvent, amide solvent or ester solvent.In some embodiments, the solvent can be supercritical fluid, such as two Carbonoxide, fluorocarbon, sulfur hexafluoride, alkane and other suitable multicomponent mixtures etc..In some embodiments, use There is relatively low boiling point in one or more solvents of the present invention, i.e. less than 160 DEG C.These solvents include but is not limited to, Tetrahydrofuran, acetone, the dioxane of Isosorbide-5-Nitrae-, DOX, ethyl acetate and methyl ethyl ketone.Available for the present invention but boiling point Other solvents more than 160 DEG C include dimethylformamide, dimethyl acetamide, 1-METHYLPYRROLIDONE, ethylene carbonate, carbon Sour propylene diester, glycerine and derivative, naphthalene and substitution form, acetic anhydride, propionic acid and propionic andydride, dimethyl sulfone, benzophenone, hexichol Sulfone, phenol, metacresol, dimethyl sulfoxide, diphenyl ether, terphenyl etc..Preferable solvent includes propylene glycol propyl ether (PGPE), 3- heptan Alcohol, 2- methyl-1-pentenes alcohol, 5- methyl -2- hexanols, 3- hexanols, 2- enanthol, 2- hexanols, 2,3- dimethyl -3- amylalcohols, propane diols Methyl ether acetate (PGMEA), ethylene glycol n-butyl ether, propylene glycol n-butyl ether (PGBE), 1_-Butoxy -2- propyl alcohol, 2- methyl - 3- amylalcohols, 2-Methoxyethyl acetate, butoxy ethanol, 2_-Ethoxyethyl group acetoacetate, 1- amylalcohols and propane diols first Ether.Further exemplary solvent includes lactate, pyruvate and glycol.Further exemplary solvent includes EP1,127, Those listed solvents in 929.Solvent listed above can be used alone or being applied in combination with two or more solvents.

In some embodiments, the reagent reacting in composition on substrate so that form the flowable thin of condensation Film.The film is flowed into gap with dielectric material blind.Then the film is converted by one or more different technologies For solid dielectric material, the technology includes thermal annealing, ultraviolet (UV) irradiation, microwave irradiation or exposed to oxidative plasma Body.According to some embodiments, the film by including but not limited to be crosslinked the precursor so as to generate solid material and/ Or remove dehydrogenation (-- H), hydroxyl (-- OH) or water (H₂O) mechanism of group is converted into solid material.In certain embodiments, it is electric Sense coupled plasma is used to convert the film.

In some embodiments, caused dielectric film or coating can carry out deposition post processing, for example, but unlimited In, corona treatment, chemical treatment, ultraviolet light, electron beam irradiation and/or the one or more performances for influenceing film Other processing.

In some embodiments, dielectric film described herein has 6 or lower dielectric constant.In these embodiment party In formula or other embodiment, film can have about 5 or lower either about 4 or lower or about 3.5 or more Low dielectric constant.However, it can be envisaged that can be formed according to the expection terminal use of film has other dielectric constants The film of (for example, higher or lower).The silicon-containing film that is formed using organic amino silane precursor described herein and method or Dielectric film has formula Si_xO_yC_zN_vH_wAn embodiment in, wherein Si scope is about 10% to about 40%, O The scope that scope is about 0% to about 65%, C is about 0% to about 75% or about 0% to about 50%, N scope It is about 0% to about 75% or about 0% to about 50%, and H scope is about 0% to about 50%, above percentage Surveyed than for atomic weight percent, wherein x+y+z+v+w=100 atomic weight percents, such as example passing through XPS or other methods Fixed.However, the other embodiment of dielectric or silicon-containing film with different formulations can use halo described herein organic Amino silane precursor is carried out.

As it was previously stated, method described herein can be used for the depositing silicon-containing films at least a portion of substrate.Properly The example of substrate include, but not limited to silicon, SiO₂、Si₃N₄, OSG, FSG, carborundum, hydrogenated silicon carbide, silicon nitride, hydrogenation Silicon nitride, carbonitride of silicium, hydrogenation carbonitride of silicium, boron nitride (boronitride), ARC, photoresist, You Jiju Compound, porous organic and inorganic materials, metal (such as copper and aluminium) and diffusion-barrier coating (such as, but not limited to, TiN, Ti (C) N, TaN, Ta (C) N, Ta, W or WN).Film is compatible with a variety of follow-up processing steps, such as, for example, chemically mechanical polishing (CMP) handled with anisotropic etching.

The film of deposition have include, but not limited to computer chip, optics, magnetic information storage, backing material or Coating, Micro Electro Mechanical System (MEMS), Nano electro-mechanical system, thin film transistor (TFT) (TFT) and liquid crystal display (LCD) on substrate Application.

In the claims, letter is used to identify claimed step (such as (a), (b) and (c)).These letters It is used to help censure method and step, the order performed without being intended to refer to claimed step, unless and only reaching this The degree that order specifically describes in the claims.

Following examples merely illustrate the method and this paper described herein for preparing the organic amino silane precursor of halo The method of the silicon-containing film of the deposition of description, and be not intended to limit the invention in any way.

Embodiment

Embodiment 1：Synthesize 2,6- lupetidine subbase chlorosilanes

In 2000ml equipped with addition 1000ml hexanes in 3 neck round-bottom flasks of mechanical agitator and charging hopper.Using Flask is cooled to -20 DEG C by dry ice IPA cryostats, and 101g (1.0mol) dichlorosilane is condensed and is dissolved in hexane.Under agitation The mixture of 113g (1.0mol) 2,6- lupetidines and 111g (1.1mol) triethylamine is added drop-wise in flask.Addition is completed Afterwards, exist_-20 DEG C of stirring reaction mixtures 1 hour, are then warming up to room temperature.Pass through the vacuum filter removal HCl in bag glove Et₃N salt byproduct precipitate, uses N₂Purge to prevent product and the reaction of moisture in air.The GC/MS of filtrate is analyzed to identify Product 2,6- lupetidine subbase chlorosilanes, the molecular ion quality for showing product are 177 and M-CH₃Support quality piece The quality of section is 162.Solvent hexane is removed by distilling, and product is separated by being evaporated in vacuo.Boiling point under 10torr is 60 DEG C, yield 66%.

Embodiment 2：The replacement synthetic route of 2,6- lupetidine subbase chlorosilanes

At -78 DEG C to 7.55g (66.68mmol) it is cis-solution of 2, the 6- lupetidines in 50mL THF is added dropwise The 2.5M hexane solutions of 28.00mL (70.02mmol) n-BuLi.Separate out and precipitate and reactant mixture heats up under agitation To room temperature.After one hour, the mixture is added dropwise to 6.74g (66.68mmol) dichlorosilanes in 30mL dimethylbenzene at -40 DEG C In the solution of 70mL hexanes, and form light grey precipitation.Reactant mixture is stirred 16 hours, afterwards by its consolidating from precipitation It is decanted and is distilled under ambient pressure to remove volatile materials in body.Product needed for 3.16g is separated, yield is 27%.Product turns out to be 2,6- lupetidine subbase chlorosilanes through GC/MS analyses.

Embodiment 3：Synthesize 2,6- lupetidine subbase dichlorosilanes

The synthesis of 2,6- lupetidine subbase dichlorosilanes by 70 weight % hexane solution with 1 part of 2,6- bis- Methyl piperidine: 1 part of triethylamine: prepared by the mixed in molar ratio of 1.1 parts of trichlorosilanes.It is double to prevent to need excessive trichlorosilane The formation of (2,6- lupetidine subbase) chlorosilane.Pass through the vacuum filter removal HClEt in bag glove₃N salt accessory substances Precipitation, uses N₂Purge to prevent product and the reaction of moisture in air.GC/MS analyses (being shown in Fig. 1) to filtrate confirm Product 2,6- lupetidine subbase dichlorosilanes are generated, display quality is 211 and-CH₃Support mass fragment quality For 196.After vacuum filter, total hexane amount is removed by the simple distillation in first step.Second step is using vacuum distillation skill Art, wherein collecting product.It is 93 DEG C that the boiling point under 18torr is determined by vacuum distillation, and the boiling point under 5torr is 66 DEG C, yield For 64%.

Embodiment 4：The ald of silicon-containing film

Use following precursor：2,6- lupetidine subbase chlorosilanes carry out the ald of silicon-containing film.Testing Deposited in the ALD processing equipments of room scale.All gas (for example, purging and reacting gas or precursor and oxygen source) are preheating to 100 DEG C, subsequently into crystallizing field.Gas and precursor flow rate use the ALD diaphragm valves with actuating at a high speed to control.Lining for deposition Bottom is 12 inches of long silicon ribbons, thermocouple is attached on sample holder to confirm underlayer temperature.Using ozone as oxygen source gas Body is deposited, and the technological parameter deposited is provided in Table II：

Table II：The technique that the ald of silicon-containing film is carried out with ozone

Repeat step b) is to e) until reaching desired thickness.The sedimentation rate of silicon-containing film caused by sign and refraction Rate.By the way that the reflectance data from film and default physical model (such as Lorentz Oscillator models) are fitted, Use the thickness and refractive index of FilmTek 2000SE ellipsometers measurement film.Film composition uses X-ray photoelectron spectroscopy (XPS) technology is analyzed.In the PHI equipped with multi-channel plate (MCD) and the Al monochromatic x-rays source focused on X-ray photoelectron spectroscopy experiment is carried out on 5000VersaProbe spectrometers.Film forms in the filmPlace measurement with Remove accidental carbon signal.The film composition of measurement eliminates hydrogen (because it can not be detected with XPS), and is normalized to 100%.

X-ray reflection meter measurement (XRR) is carried out on all samples to determine density of film.In 0.2≤2≤0.65 model The interior gate time using 0.001 step-length and 1s/ step is enclosed to scan sample.Using two-layer model analyze data, wherein will lining Bottom is defined as Si and film is defined as into silica.

As summarized in Table III, fed with the precursor of one second, using 2,6- lupetidine subbase chlorosilanes in 150- Silicon oxide film is formed under 300 DEG C of various various substrates：

Table III：The technological parameter of 2,6- lupetidine subbase chlorosilanes and the summary of result

As summarized in Table IV, fed with variable precursor, using 2,6- lupetidine subbase chlorosilanes at 300 DEG C Silicon oxide film is formed under underlayer temperature：

Table IV：The technological parameter and result of 2,6- lupetidine subbase chlorosilanes are summarized

Silicon oxide deposition is shown with the increased sedimentation rate saturation of precursor charging, shows to be similar to the atomic layer deposition from limit Product (ALD) sample behavior.As determined by x-ray photoelectron spectroscopy (XPS), deposition film have 33at.% Si and 67at.% O.Carbon, nitrogen and chlorine are not detected in the film.Density of film is 1.9 ± 0.05g/cc.

Claims

1. forming the method for dielectric film at least one surface of substrate by depositing operation, the depositing operation, which is selected from, to be changed Learning gas-phase deposition and atom layer deposition process, this method includes：

At least one surface of the substrate is provided in the reaction chamber；

Introduce the organic amino silane precursor of at least one halo；

Nitrogen source will be contained to be introduced into the reative cell, wherein the organic amino silane precursor of at least one halo and described containing nitrogen source React to provide described dielectric film at least one surface；Before the wherein described organic amino silane of at least one halo Body is selected from lupetidine subbase dichlorosilane and lupetidine subbase chlorosilane.

2. according to the method for claim 1, wherein the organic amino silane precursor of at least one halo is 2,6- diformazans Phenylpiperidines subbase dichlorosilane.

3. according to the method for claim 1, wherein the organic amino silane precursor of at least one halo is 2,6- diformazans Phenylpiperidines subbase chlorosilane.

4. according to the method for claim 1, wherein the nitrogenous source be selected from ammonia, hydrazine, nitrogen and hydrogen, ammonia plasma treatment, Nitrogen plasma, nitrogen and hydrogen plasma and its mixture.

5. according to the method for claim 1, wherein the nitrogenous source is selected from monoalkylhydrazine and dialkyl group hydrazine.

6. according to the method for claim 1, wherein the dielectric film is selected from silicon nitride and carbonitride of silicium.

7. forming the method for dielectric film by ald (ALD) technique, this method comprises the following steps：

A. substrate is provided in ALD reactors；

B. provide at least one halo organic amino silane precursor in the ALD reactors；

C. ALD reactors described in inert gas purge are used；

D. provided in the ALD reactors and contain nitrogen source；

E. ALD reactors described in inert gas purge are used；With

Repeat step b to e is until dielectric film thickness desired by acquisition；Before the wherein described organic amino silane of at least one halo Body is selected from lupetidine subbase dichlorosilane and lupetidine subbase chlorosilane.

8. according to the method for claim 7, wherein the organic amino silane precursor of at least one halo is 2,6- diformazans Phenylpiperidines subbase dichlorosilane.

9. according to the method for claim 7, wherein the organic amino silane precursor of at least one halo is 2,6- diformazans Phenylpiperidines subbase chlorosilane.

10. according to the method for claim 7, wherein the nitrogenous source is selected from ammonia, hydrazine, nitrogen, nitrogen and hydrogen, ammonia plasma Body, nitrogen plasma, nitrogen and hydrogen plasma and its mixture.

11. according to the method for claim 7, wherein the nitrogenous source is selected from monoalkylhydrazine and dialkyl group hydrazine.

12. according to the method for claim 7, wherein the dielectric film is selected from silicon nitride and carbonitride of silicium.

It is thin that 13. dielectric is formed at least one surface of substrate using plasma enhanced atomic layer deposition (PEALD) technique The method of film, this method include：

A. substrate is provided in ALD reactors；

C. ALD reactors described in inert gas purge are used；

D. plasma is provided in the ALD reactors and contains nitrogen source；

E. ALD reactors described in inert gas purge are used；With

14. according to the method for claim 13, wherein the organic amino silane precursor of at least one halo is 2,6- bis- Methylpiperidinio dichlorosilane.

15. according to the method for claim 13, wherein the organic amino silane precursor of at least one halo is 2,6- bis- Methylpiperidinio chlorosilane.

16. according to the method for claim 13, wherein the plasma is selected from ammonia plasma treatment, nitrogen plasma containing nitrogen source Body, nitrogen and hydrogen plasma and its mixture.

17. according to the method for claim 13, wherein the dielectric film is selected from silicon nitride and carbonitride of silicium.

18. the method for silicon oxide film is formed on substrate, including：

Make oxidant with the precursors reaction comprising the organic amino silane of at least one halo with described in gas-phase deposition Silicon oxide film is formed on substrate；The wherein described organic amino silane of at least one halo is selected from lupetidine subbase two Chlorosilane and lupetidine subbase chlorosilane.

19. according to the method for claim 18, wherein the vapour deposition is selected from chemical vapor deposition, ald At least one of with plasma enhanced atomic layer deposition.

20. according to the method for claim 18, wherein the vapour deposition is selected from low-pressure chemical vapor deposition, plasma At least one in body enhancing chemical vapor deposition, cyclic chemical vapor deposition and plasma enhancing cyclic chemical vapor deposition Kind.

21. according to the method for claim 18, wherein the organic amino silane of at least one halo is 2,6- dimethyl Piperidino dichlorosilane.

22. according to the method for claim 18, wherein the organic amino silane of at least one halo is 2,6- dimethyl Piperidino chlorosilane.

23. the method for forming silicon oxide film on substrate, including：

By being vapor-deposited by the composition comprising at least one organic amino silane precursor and at least one oxidant described Silicon oxide film is formed on substrate；

Wherein described vapour deposition is in chemical vapor deposition, ald and plasma enhanced atomic layer deposition It is at least one；And the wherein described organic amino silane precursor of at least one be selected from lupetidine subbase dichlorosilane and Lupetidine subbase chlorosilane.

24. according to the method for claim 23, wherein the vapour deposition is selected from low-pressure chemical vapor deposition, plasma At least one in body enhancing chemical vapor deposition, cyclic chemical vapor deposition and plasma enhancing cyclic chemical vapor deposition Kind.

25. according to the method for claim 23, wherein the organic amino silane precursor of at least one is 2,6- dimethyl Piperidino dichlorosilane.

26. according to the method for claim 23, wherein the organic amino silane precursor of at least one is 2,6- dimethyl Piperidino chlorosilane.

27. the method for forming silicon oxide film on substrate, including：

The organic amino silane of halo is introduced into reactor；

At least one oxidant is introduced into reactor, wherein, at least one oxidant and the organic amino silane of the halo React to provide silicon oxide film over the substrate；The wherein described organic amino silane of halo is selected from lupetidine Base chlorosilane and lupetidine subbase dichlorosilane.

28. for forming the method with certain thickness silicon oxide film on substrate, this method includes：

A. the organic amino silane precursor of at least one halo is introduced into settling chamber；

B. at least one organic amino silane precursor of halo described in chemisorbed is on the substrate；

C. unreacted at least one organic amino silane precursor of halo is purged using purge gas；

D. oxygen source is provided to have with least one halo adsorbed to the organic amino silane precursor of halo on the substrate of heating Machine amino silane precursors reaction；With

E. any unreacted oxygen source is optionally purged；

The wherein described organic amino silane precursor of at least one halo is selected from lupetidine subbase dichlorosilane and 2,6- Lupetidine subbase chlorosilane.

29. according to the method for claim 28, wherein repeat step a to d and optional step e, until reaching described Film thickness.

30. according to the method for claim 28, wherein the organic amino silane precursor of at least one halo is 2,6- bis- Methylpiperidinio dichlorosilane.

31. according to the method for claim 28, wherein the organic amino silane precursor of at least one halo is 2,6- bis- Methylpiperidinio chlorosilane.

32. according to the method for claim 28, it is Atomic layer deposition method.

33. according to the method for claim 28, it is plasma enhancing cyclic chemical vapor deposition method.

34. the organic amino silane precursor of halo, it is 2,6- lupetidine subbase dichlorosilanes.

35. by the depositing operation selected from chemical vapor deposition method and atom layer deposition process at least one surface of substrate The upper method for forming silicon-containing film, this method include：

Using the organic amino silane precursor of halo the silicon-containing film is formed at least one surface；Wherein described halo Organic amino silane precursor is selected from lupetidine subbase chlorosilane and lupetidine subbase dichlorosilane.

36. for the composition of deposited dielectric films, said composition includes：

A) the organic amino silane precursor of halo, selected from 2,6- lupetidine subbase chlorosilanes and 2,6- lupetidine subbase two Chlorosilane；With

B) solvent selected from ether, tertiary amine, nitrile, alkyl hydrocarbon, aromatic hydrocarbon or its mixture.

37. composition according to claim 36, wherein the solvent is tertiary amino ether.